* GB785073 (A)

Description: GB785073 (A) ? 1957-10-23

Radio frequency tuner

Description of GB785073 (A)

PATENT SPECIFICATION 785,073 Date of Application and filing Complete Specification:June I 1 1955. No 15699/55: Application made in United States of America on June 21, 1954. Complete Specification Published: Oct 23, 1957 - 151 Index at Acceptance:-Class 40 ( 8), U 18 (A 2: A 5 B 3: B 4 A). International Classification:-H 03 h. COMPLETE SPECIFICATION Radio Frequency Tuner. We, ALADDIN INDUSTRIES, INCORPORATED, : a corporation organized and operating under the laws of the State of Illinois, United States of America, of 705, Murfreesboro Road Nashville, Tennessee, United States of America do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the-following statement: - This invention relates to radio frequency tuners, particularly those adapted to tune over wide'tuning ranges at very high and ultrahigh frequencies. One principal object of the invention is to provide an improved radio frequency tuner adapted to cover a wide frequency range, such as the range from 54 to 890 megacycles, embracing the commercial television bands from 54 to 216 megacycles and from 470 to 890 miegacycles. A further object is to provide an improved tuner of the foregoing character which affords high resonant impedance. Another object is to provide an improved tuner especially well adapted to be employed as a load impedance in a radio frequency amplifier stage. Another object is to provide a wide, range radio frequency tuner

combining the advantages of high resonant impedance and a high factor of merit or Q. It is a further object to provide an improved tuner which acts generally as a variable inductance in one portion of its tuning range and as a short-circuited quarter wave line in another portion. Other objects and advantages of the invention will appear from the following description, taken with the accompanying drawing in which: Fig 1 is a longitudinal sectional view of an illustrative embodiment of the invention in the form of a wide range radio frequency tuner, the view being taken generally along the line 1-1 lPrice 3 s 6 d l in Fig 2; Fig 2 is an end elevational view of the tuner shown in Fig 1; and Vig 3 is a transverse sectional view taken generally along a line 3-3 in Fig 1 50 The illustrated tdner 1 embodies a tuning coil 2, which, as-shown, is generally helical and cylindrical In this instance, the coil is formed by a metallic ribbon or filmn 3 deposited on an insulating tubular support 4 55 and formed into the desired helical design by photographic printing or other printed circuit techniques A thin coating 5 of low-loss dielectric material may be applied to the coil 2 to protect and insulate the metallic film 3 60 To obtain adequate band spreading, particularly at the high frequency end of the tuning range covered by the tuner 1, and to minimize losses, the coil 2 is illustrated with nonuniform inductance per unit length Merely 65 by way of example, the coil 2 is shown with end portions 6 and 7 having relatively low turnum density and low inductance per unit length, together with an intermediate portion 8 having high turn density and, hence, high 70 inductance per unit length In order to minimize both the inductance and the losses in the end portion 6, the conductive ribbon 3 is made wider than in the other end portion 7 and the intermediate portion 8 The left 75 end portion 6 of the coil 2 is connected to a substantially continuous cylindrical metallic extension 9. The illustrated coil 2 is disposed in a housing 10 which may assume a variety of forms 80 but is illustrated as an elongated cylindrical tube closed at its left hand end by an end wall 11 In this instance, the coil 2 is positioned axially in the tubular housing 10 The left end of the tubular coil form 4 is mounted on 85 the end wall 11. In order to vary the inductance of the coil 2, a tuning member 12 is disposed between the housing 10 and the coil The illustrated tuning member 12 is in the form of an 90 SX t s 1 i?' ', '" 785,073 annular metallic plunger or ring having an tion, the tuner serves as the load'impedance -external-I ylindrical surface 13 closely for the radio frequency amplifier -tube 26. adjacent the interior surface of the cylindrical When input voltage at the resonant-frequency housing 10 A bore or cylindrical opening 14 of

the tuner is supplied inthe uisual way to fheis formed in the plunger 12 to receive the coil cathode 27, an output voltage is-produced at 70 2; Thus, the plunger 12 is adapted to be the anode 28: The tuner provides high telescopically received over the coil 2 and -resonant impedance throughout its tuning within the housing 10 It-is preferable to range and hence maintains the gain-of the insulate the plunger from the housing and the amplifier tube 26. coil to provide for capacitive coupling or Energy may be transferred from the tuner 75 energy transfer between the plunger and these in a variety of ways In the UHF commercial elements Accordingly, a low-loss dielectric television band, for example, energy may be sleeve 15 is interposed between the plilger efficiently transferred from the tuner 1 by and the housing 10 This sleeve 15 may take means of a coupling loop 35 disposed in the the form of a thin coating applied to the housing 10 adjacent the left end portion of the 801 plunger The insulating coatifig 5 on the coil coil 2 One end of the loop 35 is grounded to 2 insulates 'the coil from the plunger, 12 In the 4 housing in this instance, and the other addition, an air gap 16 is provided between end is brought out to a UHF output terminal the coil 2 and the plunger 36: " Provision is made for effecting relative In the VHF television band, energy may be 85 axial movement between the coil 2 and the transferred from the tuner more efficiently-by plunger 12 so as to vary the effective induct means of a lead 37 connected to the left-end ance of the coil The plunger 12 is 'adapted portion 6 of the coil 2 A coupling capacitor 38 to be moved relative to the -coil 2 in the may be connected between the lead 37 and a housing 10 by means of a cam 17 mounted on -VHF output terminal 39 90 a rotatable control shaft 18 A nnmber of By virtue of the capacitive coupling between cams may be -mounted on the shaft in order the plunger 12-and the coil 2, and between the that several tuners may be controlled in corn plunger and the housing 10, the plunger 12 mon A flexible insulating rod 19 is employed provides a low impedance path between the to connect the plunger 12 to a -pivot 20 housing 10 and the portion of the coil 2 95 mounted on a cam follower arm 21 which within the plunger This is true throughout carries a-roller 22 adapted to follow the cam the tuning range of the tuner 1 Accordingly, : 17 ' A spring 23 is -provided to bias the arm the plunger 12 acts as virtually a short circuit 21 in one direction so as to hold the roller 22 between the housing and the -portion of the against the cam 17 The flexible rod 19 corn coil inside the plunger The housing 10 acts 100 pensates for any misalignment between the as a low impedance return connection to annrm 21 and the plunger 12 A slot 24 may be ground or to some other circuit element. : formed longitudinally in the housing 10 to When-the plunger 12 is at

the extreme outer admit the arm 21 and permit movement of the ends of the coil 2 and the housing 10, as arm between the full and dotted line position shown in full lines in Fig i 1, substantially the 105 shown in Fig 1 full'inductance of the coil 2 is in the circuit Television channel numbers have been between the end lead 25 and the housing As shovn on the cam 17 to indicate-the position the plunger is moved into the housing 10ing of the cam, relative to the roller 22, -for toward its dotted line position (Fig 1), there the various-commercial television channels is a progressive decrease in the portion of the 11 Energy may be transferred to the left-hand coil effectively connected between the end-lead end of the coil 2 by means of-a -lead in the 25 and the housing Accordingly, the form of a conductive ribbon 25 connected to resonant frequency of the tuner l -is progresthe metallic cylindrical extension 9 In this sively increased It will be understood that instance, the ribbon-lead 25 is arranged to the coil 2 is resonated by distributed 115 receive energy from a grounded-grid-type capacitances between its turns and between radio frequency amplifier tube 26 having a the coil and the housing 10, together with the cathode 2-7 an anode 28, and a grid 29, the capacitance between-the anode 28-and ground, grid'being grounded by a lead 30 The ribbon and other circuit capacitances. lead 25 is connected to the anode 28 A con When the plunger reaches its dotted line 120 nection is made to the opposite end portion 7 position, shown in Fig 1, only the cylindrical of the coil by means of a lead 31, which is extension 9 of the coil is effectively connected connected through a filtering resistor 32 to a between the end lead 25 and the housing 10. terminal 33 representing a source of positive In this position the inductance in the resonant anode voltage A feed-through-type by-pass circuit is at a minimum As the plunger 125capacitor 34 is -connected between the lead 31 approaches this -position, the tuner tends to and ground The tuner '1 may be employed assume some of the characteristics of a shortin a variety of circuits and the-illustrated radio circuited resonant quarter wave line For this frequency amplifier circuit is disclosed merely reason, the Q of the tuner is maintained at a by way of example In its illustrated applica high value even at the high frequency end of 130 of the coil. 2 A wide range radio frequency tuner in accordance with claim 1, characterized in that said tuning member is in the form of a 40 plunger ring. 3 A wide range radio frequency tuner in accordance with claim 1 or 2, characterized in that said tuning member or plunger ring is insulated from said housing and from said 45 coil to provide for capacitive energy exchange therebetween to constitute a low impedance capacitive

path. 4 A wide range radio frequency tuner in accordance with claim 1, 2 or 3, characterized 50 in that said housing is provided with an end wall closing one end thereof and that said coil is supported thereon and that said tuning member is movable through the opposite open end wall of said housing and supports said 55 tubular member on the side remote from said end wall. A wide range radio frequency tuner in accordance with claim 1, 2, 3 or 4, characterized in that said housing, said tuning 60 member and said coil are circular in transverse cross-section and that means are provided at said one end of said housing for supporting a vacuum tube thereon. 6 A wide range radio frequency tuner sub 65 stantially as herein described and as illustrated in thelaccompanying drawings. HERON ROGERS AND CO, Agents for Applicants, Bridge House, 181, Queen Victoria Street, London, E C 4. the tuning range. In order to prevent adverse effects upon the performance of the tuner due to spurious resonances in the inactive portion of the coil 2, an elongated sleeve 40 is mounted on the right hand end of the plunger 12 This sleeve 40 progressively envelops the coil 2 as the plunger 12 is moved into the housing 10. Accordingly, the inactive portion of the coil :10 2, extending beyond the plunger 12, is effectively short circuited or at least heavily loaded by the sleeve 40 Any residual resonances, not completely damped out by the loading effect of the sleeve 40, are detuned to :15 frequencies far removed from the resonant frequency determined by the portion of the coil 2 between the plunger 12 and the end lead 25.

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* GB785074 (A)

Description: GB785074 (A) ? 1957-10-23

Improvements in or relating to thermal conductivity cells

Description of GB785074 (A)

COMPLETE SPECIFICATION Improvements in or relating to Thermal Conductivity Cells. We, THE BRITISH PETROLEUM COMPANY LIMITED, of Britannic House, - Finsbury Circus, London, E.C.2, a British joint-stock Corporation and Charles Leslie Arthur Harbourn and Dennis Henry Desty, both of the Company's Research Station, and both of British nationality, do hereby declare the invention for which we pray that a 'patent may be'granted to us, and the method by which it is to be performed to be particularly. described in and by the following statement: This invention relates to improved means of detecting changes- in the thermal conductivity of a gaseous stream. Detectors, employing thermal conductivity as a means of measuring the composition of gases, have been described wherein a wire is heated by an electric current, its temperature and hence its resistance varying with the conductivity of the surrounding gas. These detectors, employing hot wires, are of two main types. In the first type the hot wire is tensioned axially in a cylindrical chamber, the -gas entering-at the one end of the chamber and flowing along the wire. This type of detector suffers from two main disadvantages. The first disadvantage is that the part of the wire upon which the. gaseous stream impinges first, is appreciably cooled by- the incoming gas and thus the resistance measured will vary markedly with the rate at which the gas flows. The second is that to achieve a reasonable sensitivity- it is necessary to employ at least 3 cms. of hot wire which necessitates the use of a large chamber. This large volume hinders the resolution of closely following changes in thermal conductivity. The second type of hot wire detector employs - a small, heated, coiled wire - placed in a small side chamber connected by a single orifice to a passage through which the gas flows. This device considerably reduces the effect of change in flow rate since the gas is not directed over the wire. However, it is necessary for the gas to diffuse into the chamber before the instrument will respond and as this is a'relatimely slow process rapid changes in thermal conductivity are not easily recorded. Compared with the first described type of hot wire detector, this

second type has the advantage that the volume of the chamber is reduced but this is offset in that the response is much slower. It-has been proposed to replace the hot platinum wire in detectors hereinbefore described with - a thermistor, which is a new circuit element, a full description of which is to be found in "Electrical Engineering," Volume 65 dated November 1946, Properties and Uses of Thermistors-Thermally Sensi- tive Resistors, and in an article by W. T. Gibbons, "Thermistor Production m "Electrical Communications" for December, 1953. We have found that when using a cell containing a thermistor in place of a cell using a hot wire, the size of the chamber may be much reduced and in consequence the selectivity of the detector in the cell employing a thermistor is' increased. Furthermore it is possible, when using a thermistor, to obtain up to ten times the output voltage compared with that obtained when employing a hot wire type instrument under similar conditions. However, we have found that cells constructed according. to a general design as employed in the hot wire type cells, and wherein the hot wire is replaced by a thermistor mounted on electrical leads, are reduced in utility by their 'high sensitivity to changes in the flow rate of the gas, whereby spurious variations may be introduced into measurements of the change in thermal conductivity. The object of this invention is to provide a cell; employing a thermistor, for determining changes in thermal conductivity, having a low sensitivity to changes in flow rate. According to the-present invention there is provided: a cell for indicating variations in the thermal conductivity of a gaseous stream, comprising a thermistor mounted in a chamber n having a gas inlet and a gas outlet so arranged That a;gas~entering and leaving thereby will inflow'in ~a helical manner around the thermistor. By the term " thermistor " as used- throughout this specification and- -claims, we mean a resistor, having a high temperature coefficient, consisting of or comprising a sintered mixture of oxides. Thermistors usually have a temperature coefficient such that their resistance decreases about 4 per cent. per C rise in temperature, and have specific resistances at 20 C in the range 0.1 to 109 ohm-centimetres. Typical thermistors are (a) a mixture of manganese oxide and nickel oxide and (b) a mixture of manganese oxide, nickel oxide and cobalt oxide. Other oxides which may be employed.--'in.the thermistors include iron 'oxide (we2 0,), zinc .oxide and cuprous oxide. The preferred shape of the chamber is one having a circular cross

section, for example spherical or conical, .a convenient form being cylindrical. Owing to the small physical dimensions df the thermistor the volume of the chamber can be ~ reduced markedly; thus preferably the diameter of the circular section of the chamber is not greater than one inch whereby5 in us a high degree of resolution is obtained in measuring rapid changes in thermal conductivity in a gas stream fed thereto. Preferably the inlet and outlet are arranged to provide that, in operation, the gas is introduced tangentially at one end to the circular cross-section and at an angle to the overall path such that it completes approximately one revolution of the chamber before leaving tangentially at the other end. Conveniently, the thermistor is mounted on its electrical leads In a cylindrical chamber these leads preferably lie'along the axis of the chamber and are supported in a state of tension so that~the thermistor is held in constant position. According to a further feature of this invention there is provided an instrument for indicating variations in thermal conductivity of a gas comprising an electrical circuit having therein a cell as described hereinbefore and means - of measuring the variations in the resistance of thethermistor. This variation may be measured by incorporating a galvanometer in the circuit or it can be measured by comparing resistances in a bridge network. Furthermore this invention relates to an instrument for comparing the thermal con ductivity of two gases by using. at least two cells, the first cell being for the passage of one of the gases, and the second cell being for the passage of the other gas, the said first and second cell being connected electrically in adjacent sides of a'diferential bridge network. ~ ccbrding-~to a further development of this instrument four cells are used. The four cells are employed in pairs, each pair consisting of cells connected symmetrically and in parallel to a single inlet tube and a single outlet tube, one pair being provided for the'passage.of one gas and the other pair being provided forthe passage of the other gas, the thermistors of each pair of cells being connected electrically into non-adjacent sides of a differential bridge network. The term "gas" is used herein with - reference to single substances in the gas phase and to .gaseous mixtures. In the methods herein described for comparing gases one. of the gases may be employed in the form of a steady stream of constant composition to eliminate certain "fixed errors " arising from the use of the cell.

The invention-is illustrated but in no way limited with reference to the accompanying Figures 1-3. Figure. 1 is a vertical section through a conductivity cell. Figure 2 is a horizontal section through four conductivity cells used in an instrument for comparing variations in the thermal conductivity of two gases. Figure 3 is the electrical circuit used in an instrument for the comparison of variations in the thermal conductivity of two gases. Referring to Figure 1, the chamber 1 is cylindrical in shape, having been formed by boring a solid copper block. Inlet tube 2 enters the chamber tangentially and at such an angle that the gas completes one revolution of the chamber before leaving by the outlet tube 3 which is also tangential to the chamber and situated at the other end of the chamber to the inlet tube. Each end of the chamber is closed by a copper plug 4 having a central orifice through which the electrical leads 5 of the thermistor 6 leave the chamber. The leads are supported in insulated. copper supports 7 seated on lead washers 8. Referring to Figure 2, the conductivity cells A1,A2, A3, A4, each constructed as described with reference to Figure 1, are drilled from a solid copper Ibar with a cross-section 12" x 1", and are each 3" long and 5/16" in diameter. The inlet tubes 9 and 10 of cells A1 and A2 are joined symmetrically to a common inlet tube 11 and the outlet tubes.12 and 13 of cells A1 and A, are joined symmetrically to a common outlet tube 14. Cells. A3 and A4 are similarly joined, inlets 15 and 16 joined to common inlet 17 and outlets 18 and 19 joined to common outlet 20. Thus the two gases which are to be compared each pass through two conductivity cells arranged in parallel. Referring to Figure 3, the four conductivity cells A1, A2, A, and A4 described with reference to Figures 1 and 2 are connected electrically into a differential bridge network, in such a manner that the two cells havipg the same gas through them are in - non-adjacent sides of the bridge network. 'Between cells A2 and A, is a potentiometer 21 which is used to pre-set the balance of the network. A recording voltmeter 22 lies across the bridge from the balance point on the potentiometer to the junction 23 of cells A1 and A4. Current is supplied to the network at the junction 24 of cells A, and A4 and at the junction 25 of cells A1 and A3, the circuit supplying the current consisting of a number of voltaic cells 26 in series, a switch 27, a variable resistance 28 in series with the voltaic cells to regulate the flow of current through the thermistors and an ammeter 29.

Thermal conductivity cells and instruments comprising said cells as hereinbefore described are very suitable for determining changes in the composition of a gaseous stream. Thus the cells are particularly suitable for use as detectors in gas chromatography apparatus. Thus, for example, by the use of cells as hereinbefore described a high order of resolution has been achieved when used in conjunction with a gas chromatographic-column of the type as described by A. T. James and A. J. P. Martin in Biochem. J. Vol. 50 (1952) at page 679. Thermal conductivity cells, according to the present invention, may be used for the control of fractional distillation columns, a continuous sample of the overhead fraction, in vapour phase, being passed to one or more of said cells to permit determination of cut points, in accordance with variations in the thermal conductivity of the sample. What we claim is: 1. A cell, for indicating variations in the thermal conductivity of a gaseous stream, comprising a thermistor mounted in a chamber having a gas inlet and a gas outlet so arranged that a gas entering and leaving thereby will flow in a helical manner around the thermistor. -2. A cell according to claim 1 wherein the chamber is circular in cross section. 3. A cell according to claim 2 wherein the chamber is cylindrical. 4. A cell according to claim 3 wherein the diameter of the circular section is not grea,ter than one inch. 5. A cell according to claim 4 wherein the inlet and outlet are arranged to provide that, in operation, the gas is introduced tangentially at one end and completes approximately one revolution of the chamber before leaving tangentially at the other end. 6. A cell according to any of claims 1-5 wherein the thermistor is maintained in a constant position in the chamber by means of electrical leads held in a state of mechanical tension. 7. An instrument for indicating variation in thermal conductivity of a gas comprising a conductivity cell according to any of the preceding claims, means of passing a current through the thermistor and an indicating or recording instrument for determining variations in the resistance of the thermistor. 8. An instrument according to claim 7 wherein the conductivity cell is connected electrically in one arm of a resistance bridge network 9. An instrument for comparing the thermal conductivity of two gases comprising at least two conductivity cells according to any of claims 1-6, a first cell being provided for the passage of one of the gases and a second cell being provided for the passage of the other of the gases, said first cell and said second cell being connected electrically in adjacent sides of a differential bridge network.

10. An instrument according to claim 9 comprising two pairs of conductivity cells each pair consisting of cells connected symmetrioally and in parallel, to a single inlet tube and a single outlet tube, one pair being provided for the passage of one gas and the other pair being provided for the passage of the other gas, the thermistors of each pair of cells being connected electrically into non-adjacent sides of a differential bridge network. 11. A cell for indicating variation -in the thermal conductivity of a gaseous stream substantially as hereinbefore described with reference to the accompanying Figure 1. 12. An instrument according to claim 10 and substantially as hereinbefore described with reference to the accompanying Figures 2 and 3.

* GB785075 (A)

Description: GB785075 (A) ? 1957-10-23

Compounds of the octahydrophenanthrene series and synthesis of compounds ofthe cyclopentanodimethylpolyhydrophenanthrene series therefrom

Description of GB785075 (A)

COMPLETE SPECIFICATION Compound of the Octahydrophenanthrene Series and Synthesis of Compounds of the Cyclopentanodimethylpolyhydro- phenanthrene Series therefrom We, MONSANTO CHEMICAL COMPANY, a corporation organised under the laws of the State of Delaware, United States of America, of 1700, South Second Street, City of St. Louis, State of Missouri, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement :- This invention relates to a method of producing and to novel compounds useful in the synthesis of steroid compounds of the

cyclopentanodimethylpolyhydrophenanthrene series. The invention relates more particularly to the synthesis of 17-formyl-cyclopentano-10. 13dimethyl-9mo ~ decahydrophenanthren-3- one from l-(ss-carboxyethyl)-2-keto-14-methyl- A'ctahydrophemanthrma and its alkyi esters having up to six carbon atoms in the alkyl group. The latter are. believed to be new compounds. ~ The sequence of steps leading up to 17formyl - cyclopentano-?4.9(11)-decahydrophenanthren-3-one is outlined schematically in the accompanying drawing. The initial reactant in the process outlined in the accompanying drawing, namely-1 (hydroxy-methylene) - 2 - keto - 10-methyl1.2.5.8.9.10-hexahydronaphthalene (Compound I) contains two asymmetric carbon atoms and consequently exists in the form of four optically active isomers or two racemates, i. e. cis and trans racemic mixtures-of the dextro and laevo optically active isomers. All such forms or any mixture thereof may be employed as starting materials in the process outlined herein. Compound I is prepared by the formylation of the corresponding 2-keto-10methyl-1.2.5.8.9.10-hexahydronaphthalene <img class="EMIRef" id="026415681-00010001" /> employing ethyl formate in the presence of sodium methylate. This may be carried out in the following manner : all parts are by weight. To a reaction vessel is charged 17. 3 parts (substantially 0. 32 mols) of solid sodium methylate, 75 parts of anhydrous benzene and 37 parts (substantially 0. 5 mols) of ethyl formate while maintaining the temperature at 20-25 C. The suspension thus obtained is agitated in the presence of an) atmosphere of nitrogen for 20-30 minutes and then cooled to 10 C. : 16. 1 parts (substantially 0. 1 mols) of the laevo-rotatory form of trans-2-keto-10methyl-1. 2. 5. 8. 9. 10-hexahydronaphthalene dissolved in 150 parts of benzene is added-and the mixture agitated for 3 hours at substantially 15 C. The resulting reaction mass ig then quenched with cold dilute sulphuric acid (20 parts-of sulphuric acid in 125 parts of water) while maintaining the temperature at 15 C. and agitating for 5 minutes. The aqueous layer is separated and extracted with several small portions of benzene. The benzene extracts are combined with the original organic layer and the whole subjected to distillation under reduced pressure to remove the solvent. The light tan oily residue so obtained consists essentially (951% by weight) of the 1- (hydroxymethylene) derivative of the laevo rotatory form of trans-2-keto-10-methyl-1. 2. 5. 8. 9. 10hexahydronaphthalene. The oil is admixed with 105 parts of methanol and heated, with agitation, to 50~C. 400 parts of an aqueous 5% copper acetate solution is slowly added with constant agitation. The precipitate, namely the

copper chelate of the l- (hydroxymethylene) derivative of the laevo-xotatory form of tYans-2-keto-10-methyl-1. 2. 5. 8. 9. 10hexahydronaphthalene, is filtered off, washed with methanol, and then slurried with 87 parts of benzene. To the resulting slurry is added 1800 parts of 26% sulphuric acid. The organic layer is recovered, washed with aqueous sodiumbicarbonate, then with water and the solventremoved under reduced pressure. The. residue is the oily laevo-rotatory isomer of tracs-1- (hydroxy-methylene) - 2 - keto - 10 - methyl1.2.5.8.9.10-hexahydronaphthalene, b.p. 122123 ~C. at 2-3 mm, nD25=1.5570, [?]D25= -151. 6 (C=2, chloroform). In like manner dl-trans-l- (hydroxy- methylene)-2-keto - 10 - methyl-1.2.5.8.9.10hexahydronaphthalene was obtained from dltrans-2-keto-10-methyl-1. 2. 5. 8. 9. 10-hexa- hydronaphthalene and dl-cis-1-(hydroxy- methylene)-2-keto-10-methyl-1. 2. 5. 8. 9. 10hexahydronaphthalene from dl-cis-2-keto-10- methyl-1. 2. 5. 8. 9. 10-hexahydronaphthalene. In the first step of the process shown in the accompanying drawing Compound I is reacted with a 5-keto-6-heptenoic acid ester of the general formula <img class="EMIRef" id="026415681-00020001" /> where R is an alkyl group having up to six carbon atoms such as methyl, ethyl, propyl or butyl, in the presence of a quaternary ammonium alkoxide and an inert organic solvent-such as dioxane, isopropanol, butanol, isobutanol, tertiary butanol or pentanol. Temperatures of 0 to 60~C. can be employed but it is preferred that the reaction temperature be about 10 to 30~C. The first step-in the process, i. e. the production of the addition product Compound II is illustrated by the following : all parts are by weight. STEP I To a reaction vessel is added and intimately mixed 14.1 parts of the laevo-rotatory isomer of trans-1 - (hydroxy-methylene) - 2-keto-10methyl-1. 2. 5. 8. 9. 10-hexahydronaphthalene, 14. 9 parts of methyl 5-keto-6-heptenoate, and 15. 6 parts of tertiary butanol and the mixture cooled to 10-15 ~C. Thereupon approximately 2.4 parts of a 29.8% by weight n-butanol solution of benzyltrimethylammonium nbutoxide admixed with approximately four parts of tertiary butanol is added to the agitated mixture during 15 minutes. The mix is then held at 20-25~ C. for 16 hours, seeded with a minute amount of the final product and then held at 20-25~C, for 48 hours. To the resultant mass is added, with agitation, 25 parts of petroleum ether and the mixture cooled to about 0 C. The precipitate is filtered

off,-washed with petroleum ether, then with water and dried. The white crystalline pro duct so obtained is the laevo-rotatory isomer of trans-1-formyl-1-(31-keto-61-carbomethoxy hexyl)-2-keto-10-methyl-1. 2. 5. 8. 9. 10-hexa hydronaphth'alene (Compound n en the aocam- panying drawing when R is methyl), m.p. 66-67~C. [?]D25=-206 (C=2, chloroform). In like manner dl-trans-1-formyl-1-(31-keto 61-carbomethoxy-hexyl) - 2 - keto-10-methyl 1.2.5.8.9.10-hexahydronaphthalene is obtained from dl-trans-l-(hydroxy-methylene)-2-keto- 10-methyl-1.2.5.8.9.10-hexahydronaphthalene. In the process of Step I other quaternary ammonium-alkoxides may be employed although benzyltrimethyl ammonium n-but oxide is preferred, e.g. those having the general formula <img class="EMIRef" id="026415681-00020002" /> in which Ri, R2, Rg and R4 are alkyl or aralkyl groups and Rs is an alkyl group. Suitable alkyl groups are methyl, ethyl, propyl, butyl, amyl and octyl, and suitable aralkyl groups are benzyl and phenethyl. The preferred quaternary ammonium alkoxides are those in which R1, R2 and R3 are straight chain alkyl groups having 1-4 carbon atoms, R4 is benzyl and R5 is a branched or straight chain alkyl group having 2 to 6 carbon atoms. In the second step of the process shown in the accompanying drawing the adduct (Compound II) is heated with aqueous caustic alkali, such as sodium or potassium hydroxide, to effect ring closure followed by acidification to form a 1-(~-carboxyethyl) - 2 - keto-14methyl-?5.9.11(1)-octahydrophenanthrene (Compound III). The second step in the process is illustrated by the following : all the parts are by weight. STEP II In a reaction vessel there are intimately admixed 19 parts of 85, % potassium hydroxide, 100 parts of water, and 10 parts of the laevo-rotatory isomer of trans-1-formyl1 - (31-keto-61-carbomethoxy-hexyl) - 2 - keto10-methyl-1.2.5.8.9.10-hexahydronaphthalene. This mixture is heated to substantially 70~C. and held thereat for two hours. The aqueous solution is cooled, admixed with an equal volume of diethyl ether and the ether layer discarded. The aqueous layer is then acidified with hydrochloric acid and extracted with several portions of diethyl ether. The extracts are combined, washed with water, dried

and solvent removed under reduced pressure. The solid residue is triturated with 75 parts of a mixture of diethyl ether and petroleum ether, filtered and dried. The crystalline product so obtained is the laevo-rotatory isomer of antitrans-1-(~-carboxyethyl) - 2 - keto-14-methyl ?6.9.11(1)-octahydrophenanthrene, m.p. 101 102~C., [?]D25=-374 (C=2, chloroform). In a similar fashion. dl-anti-trans-1-(~carboxyethyl)-2-keto-14-methyl-?6.9.11(1)-octahydrop henanthrene is obtained from dl-trans1-formyl-(31 - keto - 61-carbomethoxy-hexyl)2-keto - 10 - methyl-1.2.5.8.9.10-hexahydronaphthalene. In the third step of the process shown in the accompanying drawing the carboxyl group of Compound III is esterified in an acid medium with a substantially anhydrous alkanol having up to six carbon atoms such as methanol, ethanol, isopropanol or butanol, to provide the ester Compound IV. This step may be carried out as follows: all parts are-by weight. STEP III In a reaction vessel there are intimately admixed 100 parts of the laevo-rotatory isomer of anti-trans-1-(~-carboxyethyl)-2-keto-14methyl - ?6.9.11(1)-octahydrophenanthrene, 350 parts of methyl alcohol and 17.5 parts of anhydrous hydrochloric acid. The mixture is heated at 65~C. for 4 hours. The solvent is removed under reduced pressure and the residue taken up with diethyl ether, the ethereal solution washed with aqueous sodium carbonate, then with water and then dried. Upon removal of the ether under reduced pressure a light yellow oily product, identified as the methyl ester of the laevo-rotatory isomer of anti-trans-1-(~-carboxyethyl)-2-keto14-methyl-?6.9.11(1)-octahydrophen anthrene, is obtained. Similarly the methyl ester of dl-anti-transl- (-carboxyethyl)-2-keto-14-methyl-A'- octahydrophenanthrene is obtained from dlanti-trans-1 - (~-carboxyethyl) - 2 - keto-14methyl - ?6.9.11(1) - octahydrophenanthrene and anhydrous methyl alcohol in an acid medium. Other acidic esterification catalysts may be employed, for example sulphuric acid. In the fourth step of the process shown in the accompanying drawing the keto-acid ester (Compound IV) is converted to the corresponding 6. 7-cis-glycol (Compound V) by treatment of the former with the silver salt of a low molecular weight fatty acid such as acetic acid and bromine or preferably iodine in the presence of a low molecular weight fatty acid such as acetic acid and then hydrolysing the half esters so produced with alcoholic alkali metal hydroxide. Any ethylcarbalkoxy

groups which are hydrolysed may be subsequently re esterified. This step is illustrated by the following : all parts are by weight. STEP IV 21. 6 parts of the methyl ester of the laevorotatory isomer of anti-trans-1-(~-carboxy ethyl)-2-keto - 14 - methyl-?6.9.11(1)-octahydro phenanthrene is dissolved in 794 parts of glacial acetic acid and therewith is intimately mixed 26. 0 parts of silver acetate and 18. 5 parts by weight of iodine. To the mixture is added 2. 5 parts of water and the mixture then -agitated for 1 hour at 25 C. The mixture is heated to 90-100 C. and maintained thereat for 3 hours, then cooled, filtered, and the filtrate subjected to distillation under reduced pressure to remoye the bulk of the acetic acid. The residue is taken up with 400 parts of methyl alcohol and neutralized with potassium hydroxide. To the resulting solution is added 209 parts of a 4.5% by weight methanol solution of potassium hydroxide and the mixture allowed to stand for 16 hours at 25 C. under an atmosphere of nitrogen. The solution is then neutralized with 37% hydrochloric acid and solvent removed under reduced pressure. The residue is taken up in chloroform, washed with three portions of a saturated sodium chloride solution, the washed chloroform solution dried over magnesium sulphate, then filtered and the solvent removed from the filtrate under reduced pressure. The oily residue thus obtained contains a small amount of the l evo-rotatory isomer of anti-trans-1-(B- carboxyethyl) - 2 - keto - 6.7 - dihydroxy - 14 methyl-?9.11(1)-decahydrophenanthrene but is principally its methyl ester. This residue is then taken up in anhydro ! Ua methanol and heatedimthepresenceofasmall amount of anhydrous hydrochloric acid. The solvent is removed therefrom under reduced pressure and the oily residue obtained taken up with chloroform, washed with several portions of a saturated sodium chloride solution, then with water, the chloroform solution dried over magnesium sulphate and the solvent removed therefrom under reduced pressure. The colourless oily residue is the methyl ester of the laevo-rotatory isomer of anti - trans - 1 - (~ - carboxyethyl) - 2 - keto6.7-dihydroxy - 14 - methyl-?9.11(1)-decahydrophenanthrene (Compound V in which R is methyl). In a similar manner the methyl ester of dlanti-trans-1-(~ - carboxyethyl) - 2 - keto-6.7dihydroxy-14-methyl-?9.11(1) - decahydrophenanthrene is obtained from the methyl ester of dl-anti-trans-1- ( -carboxyethyl)-2-keto-14- methyl-A'--octahydrophenanthrene.

In the fifth step of the process shown in the accompanying drawing the 6. 7-glycol (Compound V) prepared as above described is reacted with a cyclic acetal-forming ketone in the presence of a dehydrating agent. The preferred cyclic acetals (Compound VI) so produced are those obtained from the symmetrical ketones such-as acetone, diethyl ketone, cyclohexanone and para-methylcyclo- thexanone. This step is illustrated by the following : all parts are by weight. STEP V 20.8 parts of the methyl ester of the laevorotatory isomer of anti-trans-1- (~-carboxy ethyl)-2-keto-6.7-dihydroxy-14-methyl-@9.11(1)- decahydrophenanthrene prepared as described in step IV, 112 parts of anhydrous copper sulphate and 960 parts of dry acetone are -intimately mixed at room temperature for about 60 hours. The reaction mass is filtered, the filtrate treated with anhydrous potassium carbonate, filtered and the filtrate subjected to distillation under reduced pressure using a water aspirator. The residue from the distilla tion on recrystallisation from a benzene petroleum ether mixture yielded the white . crystalline laevo-rotatory isomer of the acetonide of the methyl ester of anti-trans-1 ( -carboxyethyl)-2-keto-6. 7-dihydroxy-14- methyl9 decahydrophenanthrene, m. p. 122-124 C., MD=-242. 5 (C=2, chloroform). Similarly the-acetonide of the methyl ester of dl-anti-trans-1- ( -carboxyethyl)-2-keto- 6. 7-dihydroxy--14-methy19--decahydro- phenanthrene is obtained from the methyl ester of dl-anti-trans-l-( -carboxyethyl)-2-keto-6. 7 dihydroxy-14-methyl-A'-decahydrophen- anthrene. In the sixth step of the process shown in the . accompanying drawing the 9. 10-double bond of the acetonide (Compound VI) prepared as described-above is selectively reduced with one molecular proportion of hydrogen in the pre sence of palladium. The reduction is carried out in the presence of an inert organic solvent which, is not reduced under the conditions of the reaction. Examples of such solvents are benzene, toluene, xylene, ethyl benzene, cyclo

hexane, the normally liquid alkanes and the normally liquid aliphatic alcohols. This step is illustrated by the following : all the parts are by weight. STEP VI 20 parts of the laevo-rotatory isomer of the acetonide-of the methyl ester of anti-trans-1 (~-carboxyethyl) - 2 - keto-6.7-dihydroxy-14 methyl-A''-decahydrophehantbrene pre pared as described in step V is admixed in a reaction vessel with approximately 160 parts of isopropanol, 0.3 parts of 10% aqueous sodium/ hydroxide and 4 parts of a 2.% palladium-strontium carbonate catalyst (which had been-previously reduced). While agitating, gaseous hydrogen is passed into the mixture at 25 ~C. and.at a pressure slightly above atmospheric pressure. After absorption of sub stantially one molar equivalent (approximately 0. 0535 mol) of hydrogen the catalyst is filtered off,; the filtrate neutralized with-acetic acid and the solvent removed under reduced pressure. . The residue is'taKen'up with chloroform, washed with aqueous sodium bicarbonate, then -with water, dried over magnesium sulphate and then evaporated to dryness. The white crystal line product thus obtained is the laevo-rotatory isomer of the acetonide of the methyl ester of anti-trans-1-(~ - carboxyethyl) - 2 - keto-6.7-dihydroxy-14 - methyl-@11(1) - dodecahydro- -phenanthrene, m.p. 106-108~C., [alpha;]D 25= -123~(C=2, Chloroform). In a similar manner the acetonide of the methyl ester of dl-anti-trans-1-(~-carboxyethyl)-2-keto-6.7-dihydroxy- 14 -methyl-@11(1)- dodecahydrophenanthrene is obtained by selec- -tively reducing the acetonide of the methyl ester of dl-antl-trans - 1-(~-carboxyethyl)-2 keto-6.7-dihydroxy - 14 - methyl-@ 9.11(1)-deca- hydrophenanthrene employing palladium as the hydrogenation catalyst. In the seventh step of the process shown in the accompanying drawing the acetonide (Compound VII) prepared as described above is hydrolyzed with an acid under such condi tions that the acetyl group is hydrolyzed with out substantial hydrolysis of the carbalkoxy

group to the corresponding cis-glycol (Com pound VIII), namely an alkyl ester of 1- (. P- carboxyethyl) - 2 - keto - 6.7 - dihydroxy-14 methyl-@11(1)-dodecahydrophenanthrene. This glycol is'preferably not isolated but oxidized with a lower fatty acid salt of tetravalent lead in the presence of a lower fatty acid (the eighth step of the process) to a dialdehyde, namely an alkyl ester of 1- (tO-carboxyethyl)-2- keto-5. 6-di (formylmethyl)-6-methyl-Al (9'- dctahydronaphthalene (Compound IX). This dialdehyde is dissolved in an inert solvent, for example, an aromatic hydrocarbon solvent and cyclized by heating (ninth step of the process) in the presence of a carboxylic acid salt of an organic nitrogen-containing base such as piperidine acetate to provide the correspond ing alkyl ester of 3-formyl-3a-methyl-6-( - carboxyethyl)-7-keto-A"""-octahydro- , pentanthrene (pound X). The following illustrates the preparation of the alkyl ester of 3-formyl-3a-methyl-6-(~ carboxyethyl) - 7 - keto-@ 2.5a(6) -octahydro- pentanthrene (Compound X) from the cyclic -acetal the alkyl ester of l- (-carboxyethyl)-2- keto-6. 7-dihydroxy-14-methyI-t-dodeca- hydrophenanthrene (Compound VIII) : all the parts are by weight. STEPS VII, VIII & IX 9 parts of the laevo-rotatory isomer of the acetonide of the methyl ester of anti-trans-1( -carboxyethyl)-2-keto-6. 7-dihydroxy-14- -methyI-A'-dodecahydrophenanthrene prepared as described in step VI is dissolved in approximately 60 parts of acetic acid. There upon 60 parts of water is added, intimately mixed and the solution heated on a steam bath for one ho r. The solution is cooled to 0-5 ~C. and 210 parts of water added. To the resulting solution of the cis-glycol is added at 0-5 C. 11.25 parts of lead tetra-acetate and 210 parts of acetic acid. The slurry so obtained is agitated for 10 minutes and thereto is added, with agitation, 100 parts of water. The mix ture is extracted twice using 373 parts of chloroform each time. The extracts are com -bined and washed successively with dilute 'aqueous

sodium bicarbonate, 200 parts of 1 N sulphuric acid, dilute aqueous sodium bi carbonate, and finally with water and then dried over magnesium sulphate, filtered and the filtrate distilled under reduced pressure to remove solvent. The oily residue is the dialde- hyde, which is taken up in 1350 parts of anhydrous benzene and heated to 80 C. Thereto is added, with agitation, 3 parts of acetic acid and 2 parts of piperidine. The resulting mixture is heated at 70-80 ~C. For about one hour while passing nitrogen thereover and slowly distilling the water-benzene azeotrope. The reaction mixture is cooled to room temperature, washed successively with dilute hydrochloric acid, dilute sodium bicarbonate and water, the solution dried over anhydrous magnesium sulphate and solvent distilled from the dried solution under reduced pressure. Upon recrystallization of the residue so obtained from diethyl ether, the dextro rotatory methyl ester of anti-trans-3-formyl3a-methyl-6-(~-carboxyethyl)- 7 -keto-@ 2.5a(6)- octahydropentanthrene, m.p. 70-72 ~C., is obtained. Similarly the methyl ester of dl-anti-trans-3formyl-3a-methyl-6-(~-carboxyethyl)- 7 -keto@2.5a(6) -octahydropentanthrene obtained by the acid hydrolysis of the acetonide of the methyl ester of dl-anti-trans-1-(~-carboxyethyl) - 2 - keto - 6.7-dihydroxy-14-methylA-dodecahydrophenanthrene, cleavage of the glycol so obtained and ring closure of the resulting dialdehyde. In the tenth step of the process shown in the accompanying drawing the 2. 3-double bond of the alkyl ester of 3-formyl-3a-methyl-6-(~carboxyethyl) - 7 - keto-@ 2.5a(6)-octahydropent- anthrene (Compound X) prepared as described above is selectively reduced with one molecular proportion of hydrogen in the presence of palladium to provide the alkyl ester of 3formyl-3a-methyl-6-(~-carboxyethyl)- 7 -keto@5a(6)-decahydropentanthrene (Compound XI). The reduction is carried out in the presence of an inert organic solvent, which is not reduced under the conditions of the reaction. This step is illustrated by the following : all the parts are by weight. STEP X 35. 8 parts of the dextro-rotatory methyl ester of anti-trans-3-formyl-3a-methyl-6-(~carboxyethyl) - 7 - keto-@2.5a(6) -octahydropent- anthrene prepared as described in steps VII, VIII and IX, is admixed in a reaction vessel with 800 parts of isopropanol and 15 parts of a 2% palladium-strontium carbonate catalyst (which had been previously reduced). While agitating, gaseous hydrogen is passed into the mixture at 25 ~C. and at a pressure

slightly above atmospheric pressure. After absorption of substantially one molar equivalent (approximately 0. 114 mol) of hydrogen, the catalyst is filtered off and the solvent removed under reduced pressure. The oily residue is the dextro-rotatory methyl ester of anti-trans-3- formyl-3a-methyl-6-(~-carboxyethyl) - 7-keto@5a(6)-decahydropentanthrene. In a similar manner the methyl ester of dl-anti-trans-3-formyl-3a-methyl-6- (ss- carboxyethyl)-7-keto-A'-decahydropent- anthrene is obtained from the methyl ester of dl-anti-trans-3-formyl-3a-methyl-6-(ss- carboxyethyl)-7-keto-A'-octahydropent- anthrene employing palladium as the reduction catalyst. In the eleventh step of the process shown in the accompanying drawing a cyclic ketal derived from an. alpha;~-glycol such as the monoethylene ketal, namely, an alkyl ester of 3-[21 (11.31-dioxacyclopentanyl)] - 3a - methyl-6-(~carboxyethyl) - 7 - keto-@5a(6)-decahydropent- anthrene (Compound XII), is prepared by heating an alkyl ester of 3-formyl-3a-methyl6- (-carboxyethyl)- 7-keto-A"''-decahydro-' pentanthrene prepared as described above with an. ss-glycol such as ethylene glycol in the presence of an acid condensation catalyst e. g., a toluene sulphonic acid and a water-entraining agent. This step is illustrated by the- following : all the parts are by weight. STEP XI Approximately 35 parts by weight of the dextro-rotatory isomer of the methyl ester of anti-trans-3-formyl-3a-methyl-6-(ss-carboxy- ethyl)-7-keto-A'-decahydropentanthrene prepared as in Step X is dissolved in a mixture of 2500 parts of dioxan and 4500 parts of benzene. Thereto is added and intimately mixed 7. 8 parts of ethylene glycol and 1 part of para-toluene sulphonic acid. The reaction mass is brought to reflux and the benzenewater-azeotrope slowly distilled off. Thereafter the mass is subjected to distillation under reduced pressure to remove the solvent. The residue is taken up in chloroform, and the chloroform solution washed with aqueous potassium carbonate followed by a water wash. The chloroform solution is dried and the solvent removed under reduced pressure. The residue on recrystallization from diethyl ether forms white crystals of the dextro-rotatory 3monoethylene ketal of the methyl ester anti trans-3-formyl-3a-methyl-6- (P-carboxy- ethyl)-7-keto-A"''-decahydropentanthrene, m. p. 99-101 C. In a similar manner the methyl ester of dl-anti-trans-3- [21-(11.31-dioxacyclopentanyl)] 3a-methyl - 6 - (~-carboxyethyl)-7-keto-@5a(6)- decahydropentanthrene is obtained by heating ethylene glycol with the methyl ester of dlanti-trans- 3

-formyl-3a-methyl-6-(~-carboxyethyl)-7-keto-@5a(6)-decahydropentanthre ne in the presence of an acid condensation catalyst. In the twelfth step of the process shown in the accompanying drawing an angular methyl group is introduced at the 6-position of the pentanthrene nucleus by heating methyl iodide in an inert organic solvent (or like methylating agents such as dimethyl sulphate and methyl tosylate) with the above alkyl ester e.g. the alkyl ester of 3-[21-(11.31-dioxacyclopentanyl)]3a-methyl - 6 - ~-carboxyethyl-7- keto-@5a(6)- decahydropentanthrene (Compound XII) under alkaline conditions, e. g., by adding an alkali metal alkoxide. In the introduction of the- angular methyl group an additional asymmetric carbon atom is formed and thus mixture of stereoisomers results i. e. the-and, ss-keto esters. This mixture is preferably not isolated or separated into its isomeric parts, but converted directly by hydrolysis in the presence of-water and acid (step thirteen of the syn- thesis)--to-the corresponding carboxyethyl derivative (Compound XIV). The carboxyethyl-derivative-thus obtained-is, for example, a mixture of isomeric anti-trans-3-[21-(Il. 3l- dioxacyclopentanyl)] - 3a - 6-dimethyl-6-(~carboxyethyl) - 7 keto - @5 - decahydropent- anthrene ; these isomers may be represented su ucturally and deEned as follows :- <img class="EMIRef" id="026415681-00060001" /> "-keto acid -keto acid Although both of the isomeric N and uss-keto- acids may be converted to tetracyclic ketones having the general formulas of Compounds XV, XVI and XVII of the accompanying drawing the in-eta acid gives rise to a tetracyclic ketone of the polyhydrocyclopentanophenanthrene series whose angular methyl groups are on the same side of the cyclopentanophenanthrene reference plane while the s-keto acid gives rise to a tetracyclic ketone whose angular methyl groups are on opposite sides.,j. The introduction of the angular methyl group in the : 6-position of the pentanthrene nucleus of a 3-cyclic ketal of an alkyl ester of 3-formyl - 3a.- methyl-6-(~-carboxyethyl)-7keto-@ 5a(6)-decahydropentanthrene to provide a 3-cyclic ketal of an alkyl ester of 3-formyl3a.6-dimethyl - 6 - (~-carboxyethyl)-7-ketoA5-decahydropentantbrene (for example, Compound-XIII) and conversion thereof to the free acid (for example, Compound XIV) is illustrated by the following : all-the parts are by weight. STEPS XII & XIII 12. 22 parts of dextro-rotatory mono-ethylene ketal of the methyl ester of anti-trans-3- formyl--3a-methyl--6- (a-carboxyethyl)-7- Jketo-A'-decahydropentanthrene prepared as in Step XI is dissolved in

a mixture of 360 parts of benzene and 320 parts of tertiary butanol. Thereto is added and intimately mixed 285 parts of 0.467 N potassium tertiary butoxide in tertiary butanol. While refluxing the mixture 41 parts of methyl iodide is cautiously added. Upon completion of the addition the reaction mass is refluxed for 5 minutes and then cooled to room. temperature. This-solution which contains the respective methyl-esters of the and f3-anti-trans-keto acidsinaweight ratio of approximately 1 to 2 is admixed with 200 parts of water in order to hydrolyze the esters. The organic layer is separated and extracted with dilute aqueous potassium hydroxide. The organic layer is separated and cooled to 0-3 C., admixed with an equal volume of diethyl ether and the mixture then acidifie with dilute sulphuric acid. The aqueous layer is removed and extracted with two equal volumes of diethyl ether. The ether extracts are combined, washed with water and dried. Upon removal of the ether under reduced pressure 11. 96 parts of an oil consisting of the < and {S isomers of the keto-acid in a weight ratio of approximately 1 to 2 is obtained. -The oily mixture of"-and -keto acids may be separated into its component parts by various well-known methods, for example, by dissolving the oil in a low molecular weight alkanol such as methanol, admixing therewith a chemically equivalent weight of quinine, and refluxing the reaction mass. Upon cooling to room temperature or below the respective quinine salts may be effectively separated by fractional crystallization. The quinine salts on treatment with an alkaline material more basic than quinine in an aqueous medium, followedby separation of the free quinine, and subsequently acidifying with mineral acid yields the respective-and tq-keto acids in separated form. In general, however, the mixture is not separated into its component keto-acid isomeric parts but heated (step fourteen of the process) with an organic carboxylic acid anhydride such as acetic anhydride in the presence of a catalytic amount of an alkali metal salt of the same carboxylic acid, e. g. sodium acetate. By so doing an enol lactone e.g. 3-keto-17-[21-(11.31-dioxacyclopentanyl)] cyclopentano - 10.13 - dimethyl-@ 5.9(11) -4-oxa- decahydrophenanthrene (Compound XV), is obtained as a mixture of isomers which correspond with those of the acid. This reaction is preferably carried out in an atmosphere of an inert gas. This step is illustrated by the following : all parts are by weight. STEP XIV 11. 96 parts of the oily mixture of keto-acids obtained in Step XIII is dissolved in 162 parts of acetic anhydride containing 0. 1 part of sodium acetate and renuxed for four hours under an atmosphere of

nitrogen. The reaction mass is then cooled. The acetic anhydride is removed under reduced pressure and the residue taken upwith diethyl ether. The solution is washed with aqueous sodium bi- carbonate, then with water and dried. Upon. removal of the ether under reduced pressure an oil is obtained which on standing crystallises. The yield is 9. 95 parts of a mixture of ?- and ~-enol lactones in an approximately 1 to2.weight ratio. In the fifteenth step of the process shown upon the accompanying drawing the enol lactone (Compound XV) prepared as described in steps XII and XIII is converted to the corresponding tetracyclic ketone (Compound XVI), e.g. to the mono-ethylene ketal of 3keto-17-formyl - cyclopentano-10.13-dimethyl@ 4.9(11)-decahydrophenanthrene, by reacting the former with a methyl magnesium halide at a low temperature in diethyl ether, decomposing the addition product with acid, and then heating the ether soluble product with an alcohol solution of an alkali metal hydroxide. This step affords an opportunity for conveniently separating the unwanted a-stereoisomer from the desired ss-stereoisomer since the a-stereoisomer of the enol lactone does not react in the manner indicated. This step is illustrated by the following : all the parts are by weight. STEP XV 9.95 parts of the crystalline mixture of alpha;and ~-enol lactones prepared by Step XIV is dissolved in a mixture of 500 parts of diethyl ether and 175 parts of benzene and cooled to below-50 C. Thereto is added with agitation an ether solution containing 4. 25 parts of methyl magnesium bromide while maintaining the temperature below-50 C. Upon completion of the methyl magnesium bromide addition the mixture is stirred at-50 to-55 C. for 90 minutes. Thereafter 50 parts of acetone, 60 parts of water and 20 parts of acetic acid are added and intimately mixed and the mixture permitted to rise to about 0 C. The layers are separated and the ether extract washed with aqueous sodium carbonate, then with water, dried and the ether removed under reduced pressure. The oily residue is taken up in 400 parts of methyl alcohol, 72 parts of a 16. 7l% aqueous solution of potassium hydroxide added thereto and-the mixture so obtained refluxed for 2 hours under an atmo sphere of nitrogen. Thereupon substantially all of the methanol is removed under reduced pressure. An equal volume of water is added to the residue, and the resulting mixture twice extracted with equal volumes of chloroform. The extracts are combined, dried and distilled under reduced pressure. 6. 51 parts of an oily. residue which partially crystallizes on standing is obtained. The residue is dissolved in methanol and set

aside to permit crystallization. White crystals of the optically active mono-ethylene ketal of A'"'-2l-norprogester- one, m. p. 172175 C. [a] D25=+70. 6 (C=2, chloroform), are obtained. In a similar manner the mono-ethylene ketal of white crystalline dl-@ 9(11)-21-norprogester- one is obtained by proceeding through the processes set forth in Steps XII-XV and beginning with an alkyl ester of dl-anti-trans3-[21-(11.31-dioxacyclopentanyl)] - 3a-methyl6-(~-carboxyethyl) - 7 - keto-@5a(6)-decahydro- pentanthrene. In the sixteenth and final-sep of the pro cess shown on the accompanying drawing the mono-ethylene ketal (Compound XVI) pre pared as described above is converted to the corresponding 17-formyl-cyclopentano-10.13 dimethyl-@ 4.9(11)-decahydrophenanthrene-3-one (Compound XVII) by heating the former in the presence of aqueous acid. This is illustrated by the following :. all the parts are by weight. STBP XVI 5 parts. of the mono-ethylene ketal obtained by the process of Step XV is heated with 5000 parts of 50% aqueous acetic acid at 100 C. for 90 minutes. The reaction mass is distilled under reduced pressure and the residue taken up in chloroform. The chloroform solution is washed with aqueous sodium bicarbonate and finally with water and dried. Upon removal of the chloroform an oily residue is obtained which on crystallization gives the white crystal line dextro-rotatory isomer of A"'-21-nor- progesterone, m.p. 127-131~C. Similarly dl-@9(11) - 21 - norprogesterone is obtained from the mono-ethylene ketal of dl A''-21-norprogesterone. The compound obtained by Step XVI is identical with that obtained by reacting one molar equivalent of hydrogen with the dextro rotatory isomer of @ 9(11) 16 -21-norprogesterone (m.p. 160.5-161.5 ~C.) in the presence of palladium. What we claim is :- 1.1-(~-carboxyethyl) - 2 - keto-14-methyl @ 6.9(11)1 octahydrophenanthrene) and its alkyl esters having up to six carbon atoms in the alkyl group. 2. Anti-trans-1-(~-carboxyethyl) - 2 - keto 14-methyl-@

6.9.11(1)-octahydrophenanthrene and its alkyl esters having up to six carbon-atoms in the alkyl group. 3. Laevo-anti-trans- 1 -(~-carboxyethyl)-2 keto-14 -methyl -@ 6.9.11(1) - octahydrophenanthrene and its alkyl esters. 4. The methyl ester of 1-(~-carboxyethyl) 2-keto- 14-methyl - @6.9.11(1) -.octahydrophen- anthrene. 5. The methyl ester of anti-trans-l-(, ss-carb- oxyethyl)- 2 -keto-14 -methyl - @ 6.9.11(1) - octa- hydrophenanthrene. 6. The methyl ester of Zaevo-anti-trans-1- (~-carboxyethyl) -2-keto-14-methyl- @ 6.9.11(1) -octahydrophenanthrene.

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* GB785076 (A)

Description: GB785076 (A) ? 1957-10-23

Method for packing cigarettes, cigarillos, or the like

Description of GB785076 (A)

COMPLETE SPECIFICATION Method for Packing Cigarettes, Cigarillos, or the Like. I,. KuRT-KoxER, a German Citizen, of 10 Am Pfingstberg,-Eamburg-Bergedorf, Germany, do hereby declare the invention, for which I pray that a patent may be granted to me, and the method by which it is to be performed, to be particularly described in and by the following'statement : The present invention has ; for its. object a method for packing cigarettes, cigarillos or the like in a soft packing in which a

divided part of the top closure is adapted to be closed down with the inclusion of a finger grip strip or"tearer"strip whereby this strip can be operated only by destroying a sealing element. The method according to the present invention is characterised in that a finger grip strip withdrawn from a magazineorirom'a reel is folded. around part of a cigarette block and projects to a certain extent beyond the length thereof, these operations being performed in a modified packing machine of known type or of desired-type before the cigarette block is. brought against a tin foil wrapper provided with slits or perforations at two opposed points so that the projecting end of the strip is folded in on folding the top closure in such manner that it is in the form of a loop enclosing a corner section of the top closure separated-from the-rest of the top closure by means of the slits or perforations and is arranged to lie above, the < finally folded top cl'osure and below the sealing element subsequently to be applied thereto and projects therefrom. The method can be effected on a machine designed for this method or on a normal packing'. machine with the assistance of suitable additional devices. In carrying out the method nnger grip strips are withdrawn from a withdrawal device, for example, a magazine, or from a reel with an associated severing device, byr means of a-gripper,. for example a pivota suction gripper, and these strips are laid in front of the end face of the block of cigarettes withdrawn from a cigarette magazine and are wrapped in U-form around the block on the further, movement thereof. By suitable i'mplementsjfor example cutters, the tin foil sheet leaving a tin-foil apparatus receives slits or perforations for limiting the part of the top which is lifted on opening the package. The tin foil. wrapper is then applied without closing its top, and then the liner or cover is applied whereby the finger grip strip projects from one end-of the package. After the application of a closure label on the wider side the closing of the top is effected at the narrow side whereby also tlie'finger-grip strip is laid in the form of a fold around the abutting flaps. Then the top closure is completed, the closure label is folded and the projecting part of the finger grip strip is laid on the end of the package. Finally the. package is sealed by means of a sealing element. According to further feature of the invention the closure label can be omitted if the top closure. is effected by means of adhesive on. theupperbroader,Bap or is effected by other suitable closure elements." Hereinafter the method is described on the basis of the accompanying drawing in two examples. These show in Fig. 1 the diagram of a packing machine with the individual sections A to H, Figs 2-. and 3 show

details of the. stations D to G ; Figs. 4 to 10 show packages in various working stages of the head closure with a closure label, and Figs. 11 to 16 show packages in various treatment stages. where top closure is effected by means of adhesive. According to Fig. 1 at the station A blocks of cigarettes are withdrawn from, a cigarette magazine 1 and formed to a. block 18 (see also Fig. 4) and fed towards the station B in which is located a magazine for the finger grip strips 2, whichis pivotally arranged upon a bearing 3, whereby the magazine may be moved towards and away from a rotary cross member 4 as indicated by the double cyctes & e cross member 4 withdraws the lowermost strip from the magazine which then moves away from the cross member as the latter rotates to position the strip 2 over the path of movement of the successive blocks 18. The finger grip when brought to this position is allowed to drop into'the path. of movement of said blocks andas each successive block moves forward the strip 2 is laid around the blocks 18 in the manner indicated in Fig.. 4.. A tinfoil wrapper. feed apparatus 5 of known kind is provided with cutters 6 which cut slits 19 or perforations in the tinfoil sheet 20 as shown in Fig. 4. Fig. 4 shows the moment at which a cigarette block 18 is pressed against the wrapper 20 with the finger grip strip 2 brought into-U form by the feed action. The wrapping in tinfoil without top closure and the introduction into a liner or cover 21 in the liner or-cover apparatus 7 at the station C is effected in the usual way. Fig. 5 shows the condition of the package after leaving this station. -At-the point D a normal label applying apparatus 8 applies a closure label 12, Fig. 6, on the wider side of the package the package being moved on between guides by means of the chain 17 shown in Fig. 2. The adhesion of the closure label is to be effected laterally, i. e. on the right-hand side of the slit 19, as shown in Fig. 6, so that the latter is not covered by the closure label. At the station E a carriage 9 takes over the package. On the latter there is effected in known manner by

means of-two folder blades of different lengths, the formation of the top tucks on the narrower side and at the same time part of the finger grip strip 2 is folded reentrantly about the inturned fiap, as shown at 2a, so that the package shown in Fig. 6 is produced. Thereupon the top closure is. effected by means of a reciprocating folder blade 10 and by a pivoted blade 11 at the station F and simultaneously the label 12 is folded over the end face of the package-as shown on the Fig. 7. At the same station F-a rotary brush segment 13 folds the label 12 completely down as shown in Fig. 8. Thereupon by means of a plunger 22 the end part of the finger strip 2, which so. far has projected away from the package,. is folded on to the end face of the package as shown in Fig. 9. boy the conveyor. chain 14 the packet is then supplied to a sealing element apparatus at station G which lays the sealing element 23 transversely over the finger grip strip 2 so that both the closure label 12 as also the slits 19 of the tin foil liner are covered. The finished package shown in Fig. 10 then passes to a take-off device of known kind provided at station H. From Fig. 10 it is to be seen that the finger grip strip projects by its grip end 2'past the sealing element so that on lifting this end the sealing element is torn off,, an'dq the package is opened by the corner di'vided off by the slits 19 and the cigarettes disposed in the region of this corner are lifted cut of the package. By the method according to the-second embodiment. the tin foil wrapper. receives a supply of adhesive 24 at the station B as showninFig 11. Fig 12showsthecondition after station C and Fig. 13 after passing the station E in which case of course the station D is now omitted. shows the top closure effected by adhesive. Fig. 15 corresponds to the condition of the package after station F and Fig. 16 again shows the finished package. Instead~of usirrg an adhesive'the folds of the top closure part to be held closed on opening the package can also be held together by means of interlocking folds or the like. It will be seen that the production of the packages described can be effected on known packing machines if the features described are included. In particular it is convenient to construct the device serving for applying and folding the finger grip strip as an

additional unit in order that the latter can be fitted to existing packing machines. What I claim is: 1. Method for packing. cigarettes, cigarillos or the like in. which a part of the top closure, separate from the rest of said closure, is adapted to be lifted up by means of a finger grip strip which can be operated only by destruction of a sealing element, characterised in that a finger grip strip withdrawn from a magazine or from a reel is folded around part of a cigarette block and projects to a certain extent beyond the length thereof, these operations being performed in a modified packing machine of known type or of desired type. before the cigarette block is brought against a tin foil wrapper provided with slits or perforations at two opposed points so that the projecting end of the strip is folded in on folding the top closure in such manner that it is in the form of a loop enclosing a corner section of the top closure separated. from the rest of the top closure by means of the slits or perforations and is arranged to lie above the finally folded top closure and below the sealing element sub ; sequently to be applied thereto and projects therefrom.

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* GB785077 (A)

Description: GB785077 (A) ? 1957-10-23

Improvements in electrolytic capacitors

Description of GB785077 (A)

PATENT SPECIFICATION Inventors: PAUL CRAWFORD LAKIN and ROY ALLEN CANTY 785,077 Date of Application and filing Complete Specification: July 5, 1955.

No 19414/55. Complete Specification Published: Oct 23, 1957. Index at acceptance:-Class 37, D 3 G( 1: 2: X). International Classification:-D Oll. COMPLETE SPECIFICATION Improvements in Electrolytic Capacitors We, P R MALLORY & Co INC, a company incorporated under the laws of the State of Delaware, United States of America, of Indianapolis, Indiana, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to, be performed, to be particularly described in ant by the following statement:- This invention relates generally to electrolytic capacitors and has specific application to such apparatus including means and methods for providing such capacitors adapted for use with miniaturized electrical circuits or components. In the progress of the electrical arts, especially as relating to communications and computers, electron tubes may be replaced by devices wherein electrons are controlled in a solid instead of in a vacuum, Since these devices are much smaller in physical character and structure and require different voltages applied thereto, it is desirable and often necessary that the components functionally associated with such devices be fabricated and constructed in reduced physical and electrical ratio However, the speed of development in the construction of such miniaturized electrical components in accordance with the pace of the development of crystal amplifiers known as "transistors" has presentedt a great many problems. Thus, with relation to miniaturized electric capacitors, the cooperation' of the component parts require different modes of assembly and construction As an example, the conventional structural method for sealing electrolytic capacitors such as by crimping down against a shoulder or head formed in a capacitor case, or= by crimping the case against the side of, a rubber plug, would, in non-miniaturized constructions, usually result in such a seal olccupyinfig a relatively large volume of the capacitor. Therefore; if crimping were to be used, another type of crimping construction has to be found and used so that the physical relation(Price 3 s 6 d l ships between the components of the capacitor would be regulated. The present invention meets and overcomes several of the attendant problems lcreated by the aforesaid aspects of miniaturization and affords a construction for the miniature electrolytic capacitor wherein a tight seal is obtained with very low weight loss using liquid electrolytes Moreover, the seal occupies a volume of the total capacitor volume much, less than that previously obtainable by normal

crimping methods. An object of the present invention is to provide a compact, efficient electrolytic capacitor for use with printed or miniature circuits and which is economical to fabricate and manu: facture. Another object of the present invention is to improve the construction of electrolytie capacitors especially by providing means for sealing the same so as to adapt them for utility in, small miniature type circuits. For illustrative purposes the invention will be described in connection with the accompanying drawing in which: Fig 1 is a top, plan view of the electrolytic capacitor construction of the present invention, with portions thereof broken away so as to more explicitly define the mode of assembly thereof; Figure 2 is a vertical cross-sectional view of the miniature electrolytic capacitor Iconstruction of the present invention as taken along line 2-2 thereof and as shown in Fig. 1; and Figure 3 is an expanded view of the present invention illustrating a miniaturized electrolytic capacitor as shown in the above figures. Generally speaking, the present invention provides a miniaturized electrolytic capacitor which is operable in printed and solid type amplifier circuits In the construction of a capacitor of such small dimensions it is important that the sealing construction be such that an exceedingly small portion of the entire device be used This is-necessary inasmuch as 1 ; the overall dimensions of the electrical capacitor is exceedingly small and the sealing means for such a device must, in turn, be kept within rigid volumetric limits so as to enable as much of the construction as possible to be used for the internal portion of the device, per se In the construction of the hereinafter described eldctrolytic capacitor, this is achieved by providing an internal rigid construction for the capacitor which aids in effecting the sealing of an inert electrolyte within the capacitor in such a way that very little volume is necessary for the sealing In essence, ihe capacitor includes a double container type of seal wherein one of the containers is inverted and held within its companion in such a manner that a rigid shoulder is obtained upon which a gasket may be placed-and seated A portion of the outside container is crimped over the gasket construction seated on the internal container so as to provide a rigid and substantially air-tight seal. In the Icapacitor construction, the double can construction is fabricated individually of a thin sheet of fine silver metal approximately 006 t thick The gasket material is fabricated of an elastomer and may be molded to the desired configuration At the bottom

of the outside casing a headed wire structure may be spot welded thereto so as to provide one of the terminals of the device: Referring now to the'figures of the drawing, a miniature electrolytic capacitor 10 is represented The capacitor comprises an outside metal casing 11 made from a fine sheet of silver whiclh is configured in the shape of an open ended can or cup The casing, which is adapted to act as a cathode, has elongated, side walls 12 and 13 interconnected by a bottom 14 A terminal post 15 is connected substantially at the centre of the bottom wall 14 and may be welded thereto The side walls 12 and 13 are angulated, in the assembly thereof, so as to provide tapered walls 20 and 21 which will be adapted, as hereinafter shown, to grasp and contain a molded gasket 16 adapted to aid in the sealing of the electrolytic device An, internal anode section 17, here shown, as being fabricated of tantalum, is placed within the casing of the electrolytic device. This sectionl 17 has a terminal 23 connected substantially centrally to the top thereof The terminal 23 is adapted to penetrate gasket 16 which includes an aperture 18 therethrough. Placed about the anode capacitor section i 1 an insulator tube 30 having a configuration such that it will be adapted to surround the aforesaid capacitor anode section and insulate the same from the cathode' A second or interiial casing 31, including side Wralls 35, 36 and a tfop wall 37 having a central aperture cut therethrough, is inverted within the first casing so that thf side walls are contiguous to the inside surfaces 50, 501 of side walls 12 and 13 respectively The length of the walls of the second casing is of such extent that they terminate adjacent the bottom wall 14 of the first casing 11 It is to be noted that the second casing 31 is open ended at the 70 bottom to form a cup-shaped structure with the top wall thereof having a central aperture. The gasket 16 for the electrolytic capacitor is placed between the top portions 20, 21 of the first casing 11 and the top wall 37 of 75 second casing 31 This gasket, as stated, is made of an elastomer and is preferably molded, having a punched hole centrally disposed therethrough The gasket comprises a main conical section 60 having a tapered wall 63 80 and a dependent central section 61 extending from said main section and being integrally formed or molded thereto by means of a shoulder portion 62 The extension 61 has a tapered wall 65 and is adapted by means of 85 the central aperture to circumscribe the lead or conductor 23 acting as a terminal for the electrolytic capacitor section. In the assembly of the capacitor, insulating tube 30 is first slipped over anode section 17 90 -and mashed down to insulate both ends thereof Next, the anode section, 17, covered by insulating tube 30, is

inserted in the inside cup structure 31 with its lead penetrating the small hole made in the end of the insulating 95 tube; the entire structure being pulled up snugly therein Then, the lead attached to the top, surface of the anode is forced through the centre of gasket 16 starting in the centre of the projection with the gasket being slid down 100 the lead t Q approximately,s inch from the cup. The next step is to fill the outside container 11 with an electrolyte to a predetermined level. Then the inside cup 31 and anode 17 is slowly inserted therein This is done gradually so as 105 to allow the air to escape without forcing the electrolyte out When this sub-assembly is in place, the gasket is pushed down and the outside case is crimped. As finally assembled, the second silver 110 casing extends all the way to the bottom of the first casing The gasket lies in the remaining space aboye the top wall of the second Casing and between the top portion of the first casing with the extension fitting against 115 the electfrolydtic capacitor section 17 so as to have the terminal extend centrally therethrough The container is crimped at a 45 anglie until the gasket materials are extruded or swollen out past the top portion of the 120 first casing Thus, in this construction, the rubber will be under the proper compression so as to take-care of expansion and contraction of-the containir through temperature changes for still maintaining a good seal The angle of 125 the'gasket, here determined as being 45 , is adapfed to-allow the outside container to be crimped -lightly before touching the rubber. This will then keep the gasket in plaice so that it will not push out on one side or deforan the 130 785,077 said inner casing. 2 A sealed electrolytic capacitor according

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